Herein, we studied the increasing tendency of photoacoustic (PA) conversion efficiency of the Au/polydimethylsiloxane (PDMS) composite. The thickness of the Au layer was optimized by modeling the PA process based on the Drude-Lorentz model and finite element analysis method, and corresponding results were verified. The results showed that the optimal Au thickness of the Au/PDMS composite was 35 nm. Finally, the Au/PDMS composites were coated onto the surface of aluminum alloys, which improved the thermoelastic laser ultrasonic (LU) signals to near 100 times. Besides, the defect mapping was performed by thermoelastic LU signals with Au/PDMS coating and ablation LU signals without coating; the Pearson correlation coefficient was higher than 0.95. The application in the defect detection in metal could provide guides for nondestructive detection on metals by laser ultrasound.